EP0410497B1 - Procédé pour le rinçage passif de couches de phosphates - Google Patents

Procédé pour le rinçage passif de couches de phosphates Download PDF

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Publication number
EP0410497B1
EP0410497B1 EP90201689A EP90201689A EP0410497B1 EP 0410497 B1 EP0410497 B1 EP 0410497B1 EP 90201689 A EP90201689 A EP 90201689A EP 90201689 A EP90201689 A EP 90201689A EP 0410497 B1 EP0410497 B1 EP 0410497B1
Authority
EP
European Patent Office
Prior art keywords
rinsing
aqueous solutions
rinsed
metal surfaces
passivating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90201689A
Other languages
German (de)
English (en)
Other versions
EP0410497A1 (fr
Inventor
Dieter Hauffe
Thomas Kolberg
Gerhard Müller
Horst Dr. Gehmecker
Werner Dr. Rausch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall GmbH
Original Assignee
Metallgesellschaft AG
Continentale Parker SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Metallgesellschaft AG, Continentale Parker SA filed Critical Metallgesellschaft AG
Priority to AT90201689T priority Critical patent/ATE81533T1/de
Publication of EP0410497A1 publication Critical patent/EP0410497A1/fr
Application granted granted Critical
Publication of EP0410497B1 publication Critical patent/EP0410497B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment

Definitions

  • the invention relates to a process for the passivating rinsing of phosphate layers on metals, in particular steel, galvanized steel, alloy galvanized steel and aluminum, before painting or applying adhesives using chromium-free, zirconium and fluoride-containing aqueous solutions.
  • the process of phosphating is widely used industrially to prepare metal surfaces for subsequent painting.
  • the phosphate layers generated with this cause u. a. better adhesion of the paint films to the metal, increase the corrosion resistance and inhibit the penetration of paint from damage points in the paint film when exposed to corrosion.
  • the protective properties of the phosphate layers are further improved if they are subjected to an aqueous passivating rinse.
  • the passivating rinsing agents based on hexavalent and / or trivalent chromium offer good application properties.
  • the toxicity of the tri- and especially the hexavalent chromium compounds is disadvantageous.
  • US-A-4376000 describes a chrome-free rinse aid based on polyvinylphenol. However, this must be used in a comparatively high concentration, which causes an undesirable wastewater pollution, in particular due to the high oxygen requirement required for the breakdown.
  • soluble zirconium compounds for the aftertreatment of conversion layers.
  • the rinsing agents contain alkali and ammonium as cations. The presence of alkaline earth metal cations is expressly warned. They are used at a pH of 3 to 8.5. However, these rinsing agents do not reach the quality level of the chrome-containing agents.
  • US-A-3895970 describes acidic, aqueous rinsing agents for phosphate layers based on simple or complex fluorides and names chromium zirconium fluoride and zirconium fluoride from the group of zirconium compounds. With the exception of chrome zirconium fluoride, the products mentioned in this patent only meet moderate requirements. Chromium zirconium fluoride, however, has the disadvantage of toxicity already mentioned above.
  • the object of the invention is to provide a method for passivating rinsing of phosphate layers on metals before painting or applying adhesives, which does not have the disadvantages of the known methods and is characterized by higher corrosion protection and very good paint and adhesive adhesion and the Does not pollute the environment or only to a very small extent.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the phosphated metal surfaces are rinsed with aqueous solutions, the Al / Zr / F compound with a molar ratio of Al: Zr: F of (0, 15 to 0.67): 1: (5 to 7), the total concentration of Al + Zr + F being 0.1 to 2.0 g / l and the pH adjusted to 3 to 5.
  • the phosphated metal surfaces are rinsed with aqueous solutions whose total concentration of Al + Zr + F is 0.2 to 0.8 g / l.
  • the method according to the invention is suitable for all types of phosphate layers which can be produced on metals, in particular steel, galvanized and alloy-galvanized steel, aluminized steel, zinc, zinc alloys, aluminum and aluminum alloys.
  • metals in particular steel, galvanized and alloy-galvanized steel, aluminized steel, zinc, zinc alloys, aluminum and aluminum alloys.
  • These include zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, magnesium phosphate, nickel phosphate, cobalt phosphate, zinc iron phosphate, zinc manganese phosphate, zinc calcium phosphate and other layer types with two or more divalent cations.
  • the metal surfaces are expediently rinsed with water before z. B. by dipping, spraying, flooding or rolling according to the inventive method.
  • the rinsing agents used in the process according to the invention can be chemically classified into the group of weakly acidic aluminum fluorozirconates.
  • Their manufacture can e.g. B. done so that metallic zirconium or zirconium carbonate is first dissolved in aqueous hydrofluoric acid, complex fluorozirconic acid being formed. Then metallic aluminum or aluminum hydroxide is introduced and dissolved.
  • the rinsing agents can also be prepared in other ways.
  • the phosphated metal surfaces are rinsed with aqueous solutions which additionally contain at least one of the anions benzoate, caprylate, ethylhexoate, salicylate in a total concentration of 0.05 to 0.5 g / l.
  • aqueous solutions which additionally contain at least one of the anions benzoate, caprylate, ethylhexoate, salicylate in a total concentration of 0.05 to 0.5 g / l.
  • the anions can be introduced via the corresponding acids or salts.
  • the pH of the rinse solutions is preferably adjusted with cations of volatile bases. These include in particular ammonium, ethanolammonium and di- and tri-ethanolammonium.
  • the application of the passivating rinse on the phosphated metal surfaces can be done in dipping, flooding, spraying and wetting, e.g. B. done by roller application. Treatment times are between about 1 sec to 2 min.
  • the application temperature can range from room temperature to about 80 ° C. Temperatures between 20 and 50 ° C are usually preferred. Demineralized or low-salt water is preferably used for the preparation of the rinse baths. Water with a high salt content is less suitable for bathing.
  • a further advantageous embodiment of the invention provides that the phosphated metal surfaces are rinsed with deionized water.
  • the method according to the invention is used to prepare the phosphated metal surfaces before painting or applying adhesives. It increases the adhesion of the organic films to the metallic substrate, improves the resistance of the organic films to blistering when exposed to corrosion, and inhibits corrosion penetration from damage points in the film.
  • the method has proven to be particularly advantageous in connection with cathodic electrocoating materials, powder coatings, low-solvent high-solid coatings and with coatings in which water is the main solvent.
  • Fine-crystalline, uniformly covering phosphate layers with a basis weight of 2.5 to 3 g / m 2 were produced on the three metal substrates.
  • the sheets were then rinsed with water and then rinsed passively.
  • the passivating rinsing was carried out by spraying at 30 ° C and 1 min treatment time.
  • the final treatment was a rinse with deionized water.
  • a cathodic electrodeposition primer, a filler and a topcoat were used to paint the sheets. Each layer of paint was baked separately. The total layer thickness was approx. 90 ⁇ m.
  • the rinse aid used in the process according to the invention was prepared by diluting 1.6 g of an aqueous concentrate with 0.855% Al + 8.62% Zr + 10.7% F using deionized water. The pH was then brought to 3.5-4.0 with ammonia. The rinse aid then had the following composition: 0.014 g / l Al + 0.14 g / l Zr + 0.17 g / l F + 0.026 g / l NH3.
  • the individual sample sheets were tested according to the salt spray test according to DIN 50021 SS (1008 h), the filiform test according to ASTM D 2803 (1008 h) and the General Motors Test Method TM 54-26 with 20 cycles (GM-Scab-Test).
  • the paint infiltration was measured in mm.

Claims (10)

  1. Procédé pour le postrinçage passivant de couches de phosphate sur des métaux, en particulier l'acier, l'acier zingué, l'acier zingué par alliage et l'aluminium, avant la peinture ou l'application d'adhésifs, au moyen de solutions aqueuses exemptes de chrome, contenant du zirconium et un fluorure, caractérisé en ce que l'on rince les surfaces métalliques phosphatées avec des solutions aqueuses qui contiennent un composé à base de Al/Zr/F ayant un rapport molaire Al:Zr:F de (0,15 à 0,67):1:(5 à 7), la concentration totale de AI + Zr + F allant de 0,1 à 2,0 g/l, et le pH est ajusté à 3-5.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on rince les surfaces métalliques phosphatées avec des solutions aqueuses dont la teneur totale en AI + Zr + F va de 0,2 à 0,8 g/l.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on rince les surfaces métalliques phosphatées avec des solutions aqueuses qui contiennent en outre au moins l'un des anions benzoate, caprylate, éthylhexoate, salicylate, à une concentration totale de 0,05 à 0,5 g/l.
  4. Procédé selon les revendications 1, 2 ou 3, caractérisé en ce que l'on rince les surfaces métalliques phosphatées avec des solutions aqueuses dont le pH est ajusté à l'aide de cations de bases volatiles.
  5. Procédé selon la revendication 4, caractérisé en ce que l'on rince les surfaces métalliques phosphatées avec des solutions aqueuses dont le pH est ajusté à l'aide d'ions ammonium, éthanolammonium, di- et tri-éthanolammonium.
  6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce que, à la suite du postrinçage passivant, on effectue un postrinçage avec de l'eau totalement déminéralisée.
  7. Procédé selon une ou plusieurs des revendicaons 1 à 6, caractérisé en ce que, à la suite du postrinçage passivant, on applique une peinture par cataphorèse.
  8. Procédé selon une ou plusieurs des revendications 1 à 6, caractérisé en ce que, à la suite du postrinçage passivant, on applique une peinture par poudrage.
  9. Procédé selon une ou plusieurs des revendications 1 à 6, caractérisé en ce que, à la suite du postrinçage passivant, on applique une peinture à haute teneur en solides, pauvre en solvants.
  10. Procédé selon une ou plusieurs des revendications 1 à 6, caractérisé en ce que, à la suite du postrinçage passivant, on applique une peinture avec de l'eau en tant que solvant essentiel.
EP90201689A 1989-07-28 1990-06-26 Procédé pour le rinçage passif de couches de phosphates Expired - Lifetime EP0410497B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90201689T ATE81533T1 (de) 1989-07-28 1990-06-26 Verfahren zur passivierenden nachspuelung von phosphatschichten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3924984 1989-07-28
DE3924984A DE3924984A1 (de) 1989-07-28 1989-07-28 Verfahren zur passivierenden nachspuelung von phosphatschichten

Publications (2)

Publication Number Publication Date
EP0410497A1 EP0410497A1 (fr) 1991-01-30
EP0410497B1 true EP0410497B1 (fr) 1992-10-14

Family

ID=6386020

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90201689A Expired - Lifetime EP0410497B1 (fr) 1989-07-28 1990-06-26 Procédé pour le rinçage passif de couches de phosphates

Country Status (11)

Country Link
EP (1) EP0410497B1 (fr)
JP (1) JP2909517B2 (fr)
AT (1) ATE81533T1 (fr)
BR (1) BR9003594A (fr)
CA (1) CA2018631C (fr)
DD (1) DD298436A5 (fr)
DE (2) DE3924984A1 (fr)
ES (1) ES2035699T3 (fr)
PL (1) PL164742B1 (fr)
PT (1) PT94843B (fr)
ZA (1) ZA905922B (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4017186A1 (de) * 1990-05-29 1991-12-05 Metallgesellschaft Ag Erzeugung von konversionsueberzuegen auf zink- oder zinklegierungsoberflaechen
DE4017187A1 (de) * 1990-05-29 1991-12-05 Metallgesellschaft Ag Verfahren zur nachspuelung von konversionsschichten
US5209788A (en) * 1990-11-21 1993-05-11 Ppg Industries, Inc. Non-chrome final rinse for phosphated metal
DE19511573A1 (de) * 1995-03-29 1996-10-02 Henkel Kgaa Verfahren zur Phosphatierung mit metallhaltiger Nachspülung
DE19834796A1 (de) 1998-08-01 2000-02-03 Henkel Kgaa Verfahren zur Phosphatierung, Nachspülung und kathodischer Elektrotauchlackierung
DE19854091C2 (de) * 1998-11-24 2002-07-18 Audi Ag Verfahren zur Vorbehandlung von Karosserien vor einer Lackierung
DE10010355A1 (de) * 2000-03-07 2001-09-13 Chemetall Gmbh Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile
KR20020051991A (ko) * 2000-12-23 2002-07-02 이구택 환경친화성 및 내식성이 우수한 인산염처리강판의 제조방법
CA2438718A1 (fr) 2001-02-16 2002-08-29 Henkel Kommanditgesellschaft Auf Aktien Procede de traitement d'articles polymetalliques
EP2405031A1 (fr) * 2010-07-07 2012-01-11 Mattthias Koch Procédé de revêtement d'objets profilés et objet ainsi obtenu
CN103097583B (zh) * 2010-09-15 2015-11-25 杰富意钢铁株式会社 容器用钢板及其制造方法
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
DE102016206417A1 (de) 2016-04-15 2017-10-19 Henkel Ag & Co. Kgaa Fördergestellbehandlung zur unterdrückung anlagenbedingter phosphatüberschleppung in einer prozessfolge zur tauchlackierung
DE102016206418A1 (de) * 2016-04-15 2017-10-19 Henkel Ag & Co. Kgaa Unterdrückung anlagenbedingter phosphatüberschleppung in einer prozessfolge zur tauchlackierung

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3695942A (en) * 1970-12-02 1972-10-03 Amchem Prod Zirconium rinse for phosphate coated metal surfaces
US3966502A (en) * 1972-08-17 1976-06-29 Amchem Products, Inc. Zirconium rinse for phosphate coated metal surfaces
US3852123A (en) * 1972-11-20 1974-12-03 Pennwalt Corp Sealing rinses for phosphate coatings on metal
US3895970A (en) * 1973-06-11 1975-07-22 Pennwalt Corp Sealing rinse for phosphate coatings of metal
US4496404A (en) * 1984-05-18 1985-01-29 Parker Chemical Company Composition and process for treatment of ferrous substrates
US4650526A (en) * 1986-03-18 1987-03-17 Man-Gill Chemical Company Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes

Also Published As

Publication number Publication date
DD298436A5 (de) 1992-02-20
JPH0361385A (ja) 1991-03-18
BR9003594A (pt) 1991-08-27
PT94843A (pt) 1991-04-18
CA2018631C (fr) 1999-05-11
PL164742B1 (pl) 1994-10-31
ZA905922B (en) 1992-03-25
ATE81533T1 (de) 1992-10-15
ES2035699T3 (es) 1993-04-16
PT94843B (pt) 1997-03-31
PL286243A1 (en) 1991-04-22
DE3924984A1 (de) 1991-01-31
CA2018631A1 (fr) 1991-01-28
EP0410497A1 (fr) 1991-01-30
JP2909517B2 (ja) 1999-06-23
DE59000357D1 (de) 1992-11-19

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